Organometallics

A second research area in the Sanford laboratory focuses on the design, synthesis, and reactivity studies of high valent group ten organometallic complexes (e.g., Pd(IV), Ni(III), Ni(IV) complexes). In particular, our research probes the accessibility of these complexes and their ability to mediate challenging bond-forming reactions. These species have been implicated as reactive intermediates in a variety of catalytic transformations including C–H bond functionalization, alkene difunctionalization, and cross-coupling reactions. However, their transient nature has hindered definitive characterization of their roles in catalysis. Our group rationally designs and synthesizes model complexes of these catalytic intermediates in order to directly interrogate their reactivity towards catalytically-relevant bond-forming reactions. Ultimately, a fundamental understanding of these organometallic reactions informs the optimization of known catalytic transformations and drives the development of novel catalytic reactions. Our interests in this field include:

  • The design and investigation of catalytically-relevant high-oxidation state group ten organometallic complexes
  • Mechanistic studies of fundamental organometallic reactions at these complexes
  • The application of these studies to the development of new catalytic processes

Key references:

  1. Bour, J. R.; Camasso, N. M.; Sanford, M. S. “Oxidation of NiII to NiIV with Aryl Electrophiles Enables Ni-Mediated Aryl–CF3 Coupling,” J. Am. Chem. Soc. 2015, 137, 8034-8037.
  2. Camasso, N. M.; Sanford, M. S. “Design, Synthesis, and Carbon-Heteroatom Coupling Reactions of Organometallic Nickel(IV) Complexes,” Science2015, 347, 1218-1220.
  3. Pérez-Temprano, M. H.; Racowski, J. M.; Kampf, J. W.; Sanford, M. S. “Competition Between sp3-C–N vs sp3-C–F Reductive Elimination from PdIV Complexes,” J. Am. Chem. Soc. 2014, 136, 4097-4100.
  4. Maleckis, A.; Kampf, J. W.; Sanford, M. S. “A Detailed Study of Acetate-Assisted C–H Activation at Palladium(IV) Centers,” J. Am. Chem. Soc. 2013, 135, 6618-6625.Mbofana, C. T.; Chong, E.; Lawniczak, J.; Sanford, M. S. “Iron-Catalyzed Oxyfunctionalization of Aliphatic Amines at Remote Benzylic C–H Sites,” Org. Lett. 2016, 18, 4258-4261.
  5. Cook, A. K.; Schimler, S. D.; Matzger, A. J.; Sanford, M. S. “Catalyst-Controlled Selectivity in the C–H Borylation of Methane and Ethane,” Science 2016,351, 1421-1424.
  6. Topczewski, J. T.; Cabrera, P. J.; Saper, N. I.; Sanford, M. S. “Palladium-Catalysed Transannular C–H Functionalization of Alicyclic Amines,”Nature 2016, 531, 220-224.
  7. Lee, M.; Sanford, M. S. “Platinum-Catalyzed, Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines,” J. Am. Chem. Soc. 2015, 137, 12796-12799.